Process of producing chlorids of carbon.



.No. 880,000. PATENTED MAR. a, 1908.

J. MAOKAYE.

PROGBSS FOR PRODUCING GHLORIDS OF CARBON.

1 PLI rum) 1 .1 s." I AP OATIOH A n a 190 HEETBAKEET L PATENTED MAR. 3,1908..

J. MAOKAYE. PROCESS FOR PRODUCING GHLORIDS OF CARBON.

4 SHEETSBKEET 2.

APPLICATION I'ILED APR. 13. 1905.

fiaaza ea- 75. Z

- J. MAOKAYE.

PROCESS FOR PRODUCING CHLORIDS OF CARBON.

PATENTED MAR. 3, 1908.

A PPLI O LTIOH IILED APR. 13. 1905..

' 4 SHEETBBHEET 3.

v q m a No. 880,900. PATENTED MAR. 3, 1908.

J. MAOKAYE- V PROCESS FOR PRODUCING GHLORIDS 0F GARBON.

APLIOATIOH FILED APB-.13. 1905.

4 SHEETS-SHEET 4.

UNITED STATES, PATENT OFFICE.

I JAMES MACKAYE, Ol CAMBRIDGE, MASSACHUSETTS, ASSIGNOR. TL) STONE &WEBSTER, OF

BOSTON, MASSACHUSETTS.

PROCESS FOR PRODUCING CHLOE-IDS OF CARBON.

Specification of Letter: Patent.

Application filed April 18, 1906.

Patented March 3, 1908.

' a No. 255,462.

To all whom 'it may concern:

Be it known that 1, JAMES MAOKAYE, of Cal'nbridge, in the county ofMiddlesex and State of Massachusetts, have invented certain new anduseful Improvements in Processes of Producing Chlorids of Carbon, ofwhich the following is a specification.

This invention relates to a new and imroved process for producingch'lorids of car- Figure 1 is a diagrammatic view of an apparatusconstructed in accordance with my invention. Fig. 2 is a side elevationof the reaction chamber and its stacks. Fig. 3 is a top lan view of thereaction chamber and stac s shown in Fi 2. Fig. 4 is a verticalsectional view of the reaction chamber and the connection of the chamberwith its stacks. Fig. 5 is a cross-sectional view of the reactionchamber taken on the line 5-5 of Fig. 4 lookingin the direction of thearrow. Fig. 6 is a cross-sectional view of the inlet portlon of one ofthe stacks takenon either line 6-6 of 2. Fig. 7 is a cross-sectionalview of one of the stacks taken on the line 7-7 of Fig. 2, showing thearran ement'of the divi ed portion of the stac withv its waterjacket.Fig. 8 is a view inperspective and partly in section, showing thearrangement of the divided portion of one of the stacks with its coolingchamber or water-'acket.,

In practicing my process, bring methane OIL into the presence of chlorinC1, in a closed chamber filled with porous media, preferably granulatedcoke that has been treated to remove its sulfur and iron contents. By aproper control and regulation of the reaction I am able to roducechlorids of carbon, including chloro orm, tetrachlorids of carbon, CCL,also hydrochloric acid,

H01, and various byroducts both continuousl and commercla y.

T 1e reaction where tetrachlorlds of carbon is produced may be expressedas follows:

OH, 401, CC], 4x101 Heat where -(ll-l,=methane, or the main ingredientof natural gas- (1]., chlorin, a gas-- C(ll tetrachloride of carbon, agas above- 'chlorids of carbon.

description.

T 1e methane and chlorin, if permitted to react without control, willnot produce This uncontrolled reaction may be expressed as follows:

GIL 201,, 0 4HC1 where (3H methane, C carbon, ()1, chlorin, 'HClhydrochloric acid.

While my process may be practiced in many forms 0 apparatus, I havefound the arrangement shown diagrammatically in Fig. 1 and m detail inthe other figures economical and efficient as to cost,- capacity, andsafety of operation.

Referring to 1, wherein there is illustrated diagrammatically -myimproved apparatus whereby my proces may be carried out,-1 represents agaso ter for holdin natural gas, a large percentage of which is made upof methane, as is well known. 2 represents a gasometer for holdingchlorin, 3 represents a meter, 4 a regulator, 5 a drier, 6 a 3-wayvalve, 7 a pipe leading from the gasometer 1 to the meter 3, 8 a pipeleading from the meter 3 to the regulator 4, 9 a pipe leading from theregulator 4 to the drier 5, 10 a pipe leading from the drier 5 to the3-way cock 6.

The meter 3, regulator 4, and drier 5 may he of any suitable preferreddesign or construction. the meter are well nown and require no Thepurpose of the regulator is to maintain a predetermined rate of How .ofthe contents of the gasometer 1 through the system.

12 represents a regulator, 13 a drier, 14 a pipe leading from thechlorin gasometer 2 to t e regulator 12, 15 a pipe leading from theregulator 12 to the drier 13, 16 a pipe leading from the drier 13 to a3-way cock 17. The regulator 12 is to maintain a predetermined rate offlow from the contents of the chlorin gasometer through the system. Thedrier 13 is like drier 5. I

20 represents a suitable base 'or support for holding the reactionchamber 21.

22, 23 represent stacks -each connected to one side of the reactionchamber 21, the said The pur )ose of the drier and stocks and chamberconstituting .in effect of the stack 23 and the pipe 33 leads to the endof the stack 22., By this arrangement the-methane and chlorin may bel'edto the stack 23 through the )ipes 30 and 32 or to the stack 22 throughthe pipes 31 and 325,thc purpose of this arrangement being to enable theoperator to feed the methane and chlorin as desired. The stacks 22 and23 and her 21. consist essentially of a wall of y suitable material toresist the reactions involved and are filled with any suitable material,preferably coke, which is intended to prevent the reaction heretoforereferred to, to wit:

. CH, 201 O 41ICl,

and any reaction in the mixing zone. Each of the stacks 22, 23 connectsat its lower end,

as shown in the drawings, with the bottom of chamber 21. From the top ofchamber 21 a pipe 50 leads and connects with a condenser 51.

52 represents a pipe connecting the con' denser 51 with the condenser53. A pipe 54 connects condenser 53 with condenser 55, while a pipe 56connects the condenser 55 with the pump 7, the pump acting-as an exhaustto ma tain the flow of gases through the system. The condensers 55 maybe of any suitable design or construction to hold and condense theproducts of the reaction. The reaction chamber should be maintained inany preferred wayat a tem erature between 250 and 600 C.

T e regulators 4 and 12, as shown, are connected together by shafts 12",4 and gears 4*, 12, so that thesaid regulators travel together inpredetermined order with relation to each other. Assuming the regulators4 and 12 to have 'the same capacity under the same speed and pressure,as the amount of chlorin in the mixture is reater than the amount ofmethane, the wheel 12 is made smaller than the wheel 4". When using thisarrangement above described, the ordinary water gas meter may be usedfor the regulators 4 and 12.

From the foregoing it will be seen that the system starts with twobranches, asometer 1 for the methane, gasometer 2 for the chlorin, themethane and chlorin branches uniting in the outer end of the stacks 22and 23,' the chlorin and methan being brou ht into the presence of eachother at this point. From the end of the stacks 22 or 23 the apparatusproceeds as one system up to and including the exhaust pump 57, fromwhich the uncondensed gases may be carried to any desired point. It willbe seen that the exhaust pump 57 is effective throughout the wholesystem,not only up to the chamber 21 but also through the methane andchlorin branch. At the exhaust end of the system the pressure is lessthan at the feed end, so to speak, which difference in pressure can bevaried as desired by varying the speed or work of the exhaust 57. Aninspection of the diagrammatic view shows that l have one control foreach branch, chlorin and methane, to wit, the regulators, a control forthe regulation of the heat in the reaction chamber, and a control forthe rate of work,

' to wit, the exhaust.

My process is carried out as follows: The gasom'eters 1 and 2 beingsupplied respectively with natural gas and chlorin, the cocks 6 and 17are operated to connect their respective ports with the end of the stack22 or the end of the stack-23, the purpose being to conduct both thenatural gas and the chlorin into the end of the same stack. The exhaust57 is then started. lhis compels the low of the natural gas and chlorinin predetermined quantities through their respective regulators 4 and12, into the end of the stack 22 and stack 23 where the methane andchlorin enter the material with which the stacks of the chamber arefilled, forming a mixture and thereafter passing as a mixture to thatpoint in the stack or the chamber where the temperature is suliicient topermit the desired reaction to be accomplished. In practice thetemperature for the reaction is about 400 C. but may vary from 250 to600 0., dependin upon the speed of the apparatus, the re ative purity ofthe ingredients, etc.

An desired means may be employed to estab ish in the reaction chamberthe desired temperature. As the mixture approaches the zone of reactionin the chamber, or the parts of the chamber having the requiredtemperature, the reaction begins and is completed, the products ofreaction passing out through the pipe 50. After the reaction hasstarted, the zone of reaction works back toward the end of the stack,due to the heat given off by the reaction. This phenomena enables me insome cases, to rely upon the reaction itself for the necessary'heatafter the reaction is once set up. In order to pre vent the zone ofreaction from extending too far into the stack and encroaching upon themixing zone, I employ any preferred means for so controlling thetemperature as to prevent the reaction zone from extending back into themixing zone, which rearward action if not controlled would manifestlyinterfere with the mixing and the efficiency of the apparatus and themethod. The tetrachlorid ,of carbon and hydrochloric acid together withthe other products of reaction pass, as stated, through the pipe 50 intothe condenser 51, where the gases are reduced to such a temperaturebelow 76 C. that the tetrachlorid of carbon will ,liquefy, so that itcan be drawn oil' from the condenser. For commercial purposes thetemperature of the gases should be reduced to the vicinity of 35 C. inorder to liquefy the chamber 21 with its stacks 22, 23, 6O represents apan, or other suitable receptacle, adapted to hold water and maintainedon any suitable frame or support, not shown. 61, 62 represent two slatsarranged crosswise of the pan and having a sufficient length to permittheir ends to extend beyond the sides of the pan, as shown, in order torest upon and be supported by a'suitable framework,- not shown,independent of that which supports the pan. The'lower portion of thereaction chamber is arranged between these slats, the latter each beingarranged on either side of the reaction chamber and underneath a ledgeor sidewise extension of the reaction chamber, whereby the latter issupported by the slats independent of the pan. 63 represents a barconnected at its end b bolts 64 with the underside of the slat 61 (seeFigs. 3 and 4). 65 represents a complemental slat in like mannerconnected to the underside of slat 62 by bolts 66. sent two slats, onenear each end of the pan having their ends extending beyond the edge ofthe pan and adapted to rest upon the support which carries the slats 61,62, or any other sup'port independent of the support of the pan. 69represents a slat connected at its ends by bolts 70, to the underside ofthe slat 67 (see Fig. 2). 71 represents a slat connected at itsends bybolts 72 to the underside of the slats 68. The slats 61, 62 serve tosupport the reaction chamber and at the same time the slats 63, 65, thelatter together. with. the slats 69 and 71 serving to sup ort inclinedlongitudinal slats 73. Three of the slats 73 are arranged at one end ofthe pan, three at the other, each set of three slats forming in effect agrid, one set of the slats or grid supporting the inclined part 22 ofthe stack 22, while the other set of slats on the righthand end of thepan support the incllned part 23 of the stack 23.

By the described construction it will be seen that the water circulationcan be maintained about the inclined parts 22*, 23 of the stacksand thelower part of the reaction chamber 21. The lower part of the stack 23immediately above the inclined part 23 is divided, as shown in Figs. 2,7, and 8, for a short distance to subdivide the cross-sectional area ofthe stack and increase the cooling surface by means of the chamber 76.

' 77 represents a water-jacket of any suit- 67, 68 reprepasses, but maybe open at the top, and water circulation may be maintained in thischamber about the two branches 120, 121,-of the stacks and throu h thechamber 76 between said branches y any desired means. The stack 22 mayif desired be formed with a like subdivision provided with a likewaterjacket, it being understood that the circulation in the pan 77 isor may be inde endent of the circulation in the pan 60. EVhile I haveshown in the drawings a stack divided into two branches, suchsubdivision may be made into anydesired number of branches, the ideabeing to subdivide the stack into a suflicient number of branches toenable the cooling media to maintain the desired temperature bydissipating the heat of the reaction. The upper end of the stack 23 isclosed and rovided with three inlet ports 80, 81, 82, tlie latter beingfor methane or natural gas and the ports 80, 81 for chlorin. Twodiaphragms 83, 84, are arranged one on either side of the port 82 andextend down a substantial distance into the stack, permitting thenatural gas to enter the stack, but keeping it separate from the chlorinwhich enters throug the ports 81, on either side respectively of thediaphragms 84, 83. The stack 22 in like manner is provided with ports86, 87, for the chlorin and the port 88 for the natural gas. The stack22 is further provided with diaphragms ,89 and 90, corre sponding to thediaphragms 83, 84. Each of the stacks and their branches 22", 23 arefilled .with. pulverized material 100 of any suitable kind to permit themixing of the chlorin and natural gas without explosion. I have found inpractice pulverized coke very satisfactory for this purpose, care,however, being exercised not to have the coke pulverized so fine as tocreate powder to cause back pressure. The coke 100 in each stack extendssubstantially up to the point indicated by line 6'6, that is, above thelower ends of the diaphragms 83 to 84 and to 89 so that the chlorin andnatural gas are in contact with coke or other material before they comein contact with each other. I

The reaction chamber. 21 is composed of a piece of soap-stone 90,through which is out a rectangular hole (see. Figs. 4 and 5) and isfilled with powdered coke 100. \Vhile any desired material may be usedfor the body of the chamber, I have found soap-stone very .efiicient towithstand the various phenomena attendant upon the reaction that takesplace,

as well as the action of the mixture and the products of the' reaction.The sides of the soa stone block 90 are preferably covered with lead 92,which, at the bottom is bent under the lower end of the block, as shownin Fig. 4, then extended downward a short distance and then bent at anangle and extend ed to form the inclines 22, :23, and the stacks .22 and23, thus making the chamber, the soap-stone and the stacks eontinuous.

97 (Fig. 4) represents a block of lead ar' ranged in a pocket formed bythe lead covering 02 and serves as a terminal. This block, as shown, isrectangular in shape and extends the whole length of the chamber, whichat this point is of lead.

102 103 represent a row of carbon rods, one on either side of thechamber in the soapstone. The lower ends of these rods are arranged incomplemental recesses in the lead terminal 07. lheupper ends of the rowof rods 103 are arranged in the carbon terminal 104 at the t0 of thechamber, while the upper ends of t \e rods 102-are arranged in thecarbon terminal 105.

106 represents a carbon strip arranged between the two terminals 105,104, and provided with a marginal lip, as shown, engaging the tops ofthe termina s in order to prevent its slipping downward.

110 represents a dome formed of lead arranged over the carbon strip 106,as shown, and over the chamber in the soa )-stone. The ends of the sheetof lead forming this dome are carried down and inserted in a suitablerecess in the soap-stone, as shown in Fig. 4. The upper edge of thesheet of lead 92 that covers the soap-stone is not turned down, in orderto prevent any contact between this and the lead forming the dome.

112, 113 represent two bars one on either side and at the lower part ofthe dome. These bars are ada ted to be clamped to gether bymeansof )olts115 at each end, in order to bind the parts firmly in position, thecarbon strip 106 serving as an abutment against which the terminals 104can be pressed. 1

116 represents a wire running from the top of the dome 110 to anysuitable source of power.

117 represents a wire running from one of the inclined members of thestacks, here shown as 23, to the source of power, the current passingfrom the source of ower to the stack, thence to the lead termina 97,through the rods 102, 103 to the terminals 104, 105, to the dome 110,thence back. Any suitable instrumentalities, such as a switch,rheostats, etc., may be employed to regulate the current.

While I have made use of the term tetrachlorid of carbon as descriptiveof the products of reaction, as carried on in my apparatus and by myprocess, I wish it understood that I have used such term by way ofillustration, and not in any sense byway of limitation, since my processand apparatus are designed and intended for the production of allchlorids of carbon, including chloroform.

Having thus explained the nature of my invention and described a way ofconstructing and using the same, though without attempting to set forthall of the forms in which it may be made, or all of the lnodes of itsuse, what I claim and desire to secure by Letters Patent is:

1. The process of producing chlorids of carbon which consists in mixinggas and chlorin in the presence of a porous media, subjecting saidmixture to a reacting temperature, maintaining the mixing zone separatefrom the reacting zone, and separating the products of reaction.

2. The process of producing chlorids of carbon which consists in mixinggas and chlorin in the-presence of a porous media, preventing reactionin the mixing zone, subjecting said mixture to a reacting temperature,and separating the products of reaction.

3. The: process of producing chlorids of carbon which consists in mixinggas and chlorin in the presence of a porous media, subjecting saidmixture to a predetermined temperature by electrical means, maintainingthe mixing zone separate from the reacting zone and separating theproducts of reaction.

4. The process of producing chlorids of carbon which consists in mixinggas and chlorin in the presence of granulated coke, subjecting saidmixture to a reacting temperature, maintaining the mixing zone separatefrom the reacting zone, controlling the tern eratures of both zones, andexhausting at the delivery end of said reacting zone to maintain auniform action and separating the products of reaction.

5. The process of producing chlorids of carbon which consists in mixinggas and chlorin in the presence of a porous media, subjecting saidmixture to a reacting temperature, controlling the temperatures of themixing and the reacting zones, maintaining the reacting and mixing zonesseparate, and separating the products of reaction.

6. The process of producing chlorids of carbon which consists inbringing natural gas and chlorin together in a closed chamber containinggranulated coke, controlling the temperature of said chamber, subjectingsaid mixture to a reacting temperature, maintaining the reaction zoneseparate from the mixing zone, regulating the temperatures of the mixingzone and reacting zone, and separating the products of reaction.

7'. The process of producing chlorids of carbon which consists ofbringing natural gas and chlorin together continuously in a closedchamber containing granulated coke, exhausting said mixture from saidchamber to a reacting chamber, subjecting said mixture in the reactingchamber to a reacting temperature, controlling the location or zone ofreaction with reference to the zone of mixing, controlling thetemlperatures of both said chamber, subjecting said mixture to a zones,exhausting at the de ivery end of said reactingtemperature, controllingthe temreaction zone to maintain a uniform and peratures in the mixinand reacting zones, continuous action, and separating the prod andseparating the pro ucts of reaction. 15 ucts of reaction. In testimonywhereof I have aflixed my 8. The rocess of producing chlorids ofsignature, in presence of two witnesses.

carbon which consists in mixing natural gas and chlorin in a closedchamber in the pres- JAMES MAGKAYE' ence of a granulated porous media,control- Witnesses:

ling the temperature of said chamber, ex- H. L. ROBBINS,

hausting said mixture to a reaction zone in WILLIAM QUINBY.

DISCLAIMER.

-880,900.--James MacKag e, Cambridge, Mass. Pnocnss non PRODUCINGCanonms or CARBON. Patent dated March 3, 1908. Disclaimer filed June 1,1908, by the assignees.

Enter their disclaimer- As not within the invention claimed in claimsone to five of said Letters Patent to any and all processes forproducing chlorids of carbon in which the gas mixed with chlorin underthe conditions set out in said several claims respectively is other thanthe carbon-bearin g gas referred to in the specification-namely,methane, (CH,) whether pure or, as in the case of natural gas, mixedwith other gases not materially interfering with the action of themethane.[ Oficial Gazette, June 9, 1908.]

Disclaimer in Letters Patent No. 880,900.

said chamber, subjecting said mixture to a reactingtemperature,controlling the temperatures in the mixin and reacting zones, andseparating the pro ucts of reaction.

In testimony whereof I have aflixed my signature, in presence of twowitnesses.

JAMES MAoKAYE.

Witnesses:

H. L. ROBBINS, WILLIAM QUmBY.

DISCLAIMER.

Pnocnss I on PRODUCING CBLORIDs or Disclaimer filed June 1, 1908, by the-880,900.--James MacKaye, Cambridge, Mass. CARBON. Patent dated March 3,1908. assignees. I

i Enter their disclaimer- As not within the invention claimed in claimsone to five of said Letters Patent to i any and all I I several claimsrespectively is other than the carbon-bearm g gas referred to in thespecification-namely, methane, (CH,) whether pure or, as 1n the case ofnatural gas, mixed with other gases not materially interfering with theaction of the methane.[ Oficial Gazette, June 9, 1908.]

Disclaimer in Letters Patent No. 880,900.

CARBON. Patent dated March 3, 1908. Disclaimer filed June 1, 1908, bythe assignees.

Enter their disclaimer- As not within the invention claimed in claimsone to five of said Letters Patent to any and all processes forproducing chlorids of carbon in which the gas mixed with ehlorin underthe conditions set out in said several claims respectively is other thanthe carbon-bearing gas referred to in the specification-namely, methane,(CH whether pure or, as in the ease of natural gas, mixed with othergases not materially interfering DISCLAIMER. i l

l I with the action of the methane.-[ Ojficial Gazette, June 9, 1908.]

Disclaimer in Letters Patent No. 880,900.

-880,900.--Jamea MacKaye, Cambridge, Mass. Paocnes FOB Pnonuome CnLomDeor

